JPH0334776B2 - - Google Patents
Info
- Publication number
- JPH0334776B2 JPH0334776B2 JP59006101A JP610184A JPH0334776B2 JP H0334776 B2 JPH0334776 B2 JP H0334776B2 JP 59006101 A JP59006101 A JP 59006101A JP 610184 A JP610184 A JP 610184A JP H0334776 B2 JPH0334776 B2 JP H0334776B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin
- polyvinylidene fluoride
- ethylene
- vinyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 7
- 230000005865 ionizing radiation Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- JFZBUNLOTDDXNY-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)OCC(C)OC(=O)C(C)=C JFZBUNLOTDDXNY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PLGOYNXHSRQDOG-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(CO)(CO)CO PLGOYNXHSRQDOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- SWHLOXLFJPTYTL-UHFFFAOYSA-N [2-methyl-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(COC(=O)C(C)=C)COC(=O)C(C)=C SWHLOXLFJPTYTL-UHFFFAOYSA-N 0.000 description 1
- HSZUHSXXAOWGQY-UHFFFAOYSA-N [2-methyl-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)COC(=O)C=C HSZUHSXXAOWGQY-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- YLTDNYQTDYMOBH-UHFFFAOYSA-N bis(prop-2-enyl) 2-hydroxybutanedioate Chemical compound C=CCOC(=O)C(O)CC(=O)OCC=C YLTDNYQTDYMOBH-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
［発明の背景と目的］
本発明は、可撓性、透明性および難燃性に優れ
た架橋成形体の製造方法に関するものである。
例えば、機器内配線の接続や端末処理の用途に
熱収縮チユーブを用いる場合、接続部の状態が目
視できることから透明性に優れたものが、また、
取扱い易さの点から可撓性に富むことが、さら
に、火災時を考慮して難燃性を有することが要求
されている。
従つて、この分野の用途には従来より透明性に
優れ、難燃性であるポリ塩化ビニル樹脂が用いら
れている。この場合、可撓性を付与するために添
加した可塑剤がにじみ出して機器表面を汚染した
り、チユーブの被着体である絶縁電線に可塑剤が
移行することが多く、可塑剤を使用しない無可塑
タイプの熱収縮チユーブが望まれていた。
しかし、無可塑タイプの樹脂であるポリエチレ
ンまたはエチレンを主体とする共重合体は難燃性
に劣り、難燃化するために難燃剤を添加すると透
明性が損なわれてしまう。また、ポリふつ化ビニ
リデン樹脂は難燃性および透明性に優れているが
硬いため可動部への使用に適さない。
本発明は、上記に基づいたもので、可撓性、透
明性および難燃性に優れた架橋成形体の提供を目
的とするものである。
［発明の概要］
本発明は、エチレン−酢酸ビニル共重合体と多
官能モノマを混合し、次いでこの混合物とポリふ
つ化ビニリデン樹脂を混合することにより、エチ
レン−酢酸ビニル共重合体20〜80重量％とポリふ
つ化ビニリデン樹脂80〜20重量％を含む樹脂成分
100重量部に対して多官能モノマを0.5〜15重量部
含有する樹脂組成物を調整し、当該樹脂組成物を
成形してから電離性放射線の照射により架橋する
ことを特徴とするものである。
本発明において、エチレン−酢酸ビニル共重合
体は、ポリふつ化ビニリデン樹脂の透明性および
難燃性を損なうことなく可撓性を付与するために
配合されるものである。エチレン−酢酸ビニル共
重合体とポリふつ化ビニリデン樹脂の配合割合
は、重量比で20〜80／80〜20とする必要があり、
エチレン−酢酸ビニル共重合体の量が20重量％以
下であると十分な可撓性を得ることができず、80
重量％を越えると難燃性が低下することになる。
多官能モノマは成形体の架橋効率を向上させる
ために添加するもので、エチレン−酢酸ビニル共
重合体とポリふつ化ビニリデン樹脂からなる樹脂
成分100重量部に対して0.5〜15重量部添加する必
要がある。多官能モノマの添加量が0.5重量部以
下では十分な架橋度を達成できず、15重量部程度
で架橋度の向上効果は飽和する。
多官能モノマとしては、アクリレート類（ジエ
チレングリコールジアクリレート等）、ジメタア
クリレート類（ジエチレングリコールジメタアク
リレート、ジプロピレングリコールジメタアクリ
レート等）、トリアクリレート類（トリメチロー
ルエタントリアクリレート、トリメチロールブタ
ントリアクリレート等）、トリメタアクリレート
類（トリメチロールエタントリメタアクリレー
ト、トリメチロールプロパントリメタアクリレー
ト等）、トリアリルシアヌレート、トリアリルイ
ソシアヌレート、ジアリルマレート等があげられ
る。
なお、多官能モノマは、ポリふつ化ビニリデン
樹脂には均一に分散しにくいため、エチレン−酢
酸ビニル共重合体に多官能モノマを練り込んで均
一に混合し、この混合物をポリふつ化ビニリデン
樹脂とともにタンブラー等の混合機で均一に混合
することが必要である。
エチレン−酢酸ビニル共重合体、ポリふつ化ビ
ニリデン樹脂および多官能モノマを含有する樹脂
組成物は、押出機により所定形状に成形され、そ
の後電子線等の電離性放射線の照射により架橋さ
れる。
本発明は、種々の架橋成形体の製造に適用可能
であるが、特に、熱収縮チユーブの製造に好適で
ある。熱収縮チユーブは、チユーブを軟化点もし
くは融点以上の温度で膨張させ、そのまま冷却す
ることによつて製造されるが、軟化点もしくは融
点以上の温度では樹脂が溶融するためチユーブを
膨張することができない。このため、チユーブが
溶融しないように架橋がなされる。架橋方法とし
ては、化学架橋、電離性放射線照射架橋等がある
が、ポリふつ化ビニリデン樹脂の成形温度に耐え
る有機過酸化物が存在しないため化学架橋は不可
能である。従つて、本発明では電離性放射線の照
射による架橋が採用される。
［発明の実施例］
第１表に示すような各種成分を含有する樹脂組
成物を調整した。この場合、エチレン−酢酸ビニ
ル共重合体と多官能モノマ（トリメチロールプロ
パントリメタクリレート、トリアリルイソシアヌ
レート）を均一に混合し、その後ポリふつ化ビニ
リデン樹脂と混合した。
上記樹脂組成物をプレスによりシート成形し、
電子線加速器照射して架橋した。
各例のシートについての評価結果は、第１表の
下欄に示す通りである。
なお、評価は次に基づいて行なつた。
燃焼試験：厚さ２mmのシートに1.5MeVの電子線
加速器で5Mrad照射した後、ASTMD635に基づ
いて評価した。
透明性：厚さ0.5mmのシートに1.5MeVの電子線加
速器で5Mrad照射した後、目視により肉眼で判
定した。
可撓性（スキヤントモジユラス）：厚さ0.5mmのシ
ートに1.5MeVの電子線加速器で5Mrad照射した
後、UL224に基づいて試験した。判定は、UL224
の可撓性タイプの判定基準に準拠した。
[Background and Objectives of the Invention] The present invention relates to a method for producing a crosslinked molded article having excellent flexibility, transparency, and flame retardancy. For example, when using heat-shrinkable tubes to connect internal wiring in equipment or to process terminals, it is better to use heat-shrinkable tubes that have excellent transparency because the condition of the connections can be visually checked.
It is required to be highly flexible for ease of handling, and to be flame retardant in the event of a fire. Therefore, polyvinyl chloride resins, which have excellent transparency and flame retardancy, have been used for applications in this field. In this case, the plasticizer added to give flexibility often oozes out and contaminates the equipment surface, or the plasticizer transfers to the insulated wire that is the adherend of the tube, so no plasticizer is used. A non-plastic type heat shrinkable tube was desired. However, polyethylene, which is a non-plastic type resin, or a copolymer mainly composed of ethylene has poor flame retardancy, and when a flame retardant is added to make it flame retardant, transparency is impaired. Further, although polyvinylidene fluoride resin has excellent flame retardancy and transparency, it is hard and therefore not suitable for use in moving parts. The present invention is based on the above, and aims to provide a crosslinked molded article having excellent flexibility, transparency, and flame retardancy. [Summary of the Invention] The present invention comprises mixing an ethylene-vinyl acetate copolymer and a polyfunctional monomer, and then mixing this mixture with a polyvinylidene fluoride resin to produce an ethylene-vinyl acetate copolymer of 20 to 80% by weight. % and polyvinylidene fluoride resin 80-20% by weight resin component
The method is characterized in that a resin composition containing 0.5 to 15 parts by weight of a polyfunctional monomer per 100 parts by weight is prepared, the resin composition is molded, and then crosslinked by irradiation with ionizing radiation. In the present invention, the ethylene-vinyl acetate copolymer is blended to impart flexibility to the polyvinylidene fluoride resin without impairing its transparency and flame retardancy. The mixing ratio of ethylene-vinyl acetate copolymer and polyvinylidene fluoride resin must be 20-80/80-20 by weight.
If the amount of ethylene-vinyl acetate copolymer is less than 20% by weight, sufficient flexibility cannot be obtained, and 80
If the content exceeds % by weight, the flame retardancy will decrease. The polyfunctional monomer is added to improve the crosslinking efficiency of the molded product, and must be added in an amount of 0.5 to 15 parts by weight per 100 parts by weight of the resin component consisting of ethylene-vinyl acetate copolymer and polyvinylidene fluoride resin. There is. If the amount of the polyfunctional monomer added is less than 0.5 parts by weight, a sufficient degree of crosslinking cannot be achieved, and the effect of improving the degree of crosslinking is saturated at about 15 parts by weight. Examples of polyfunctional monomers include acrylates (diethylene glycol diacrylate, etc.), dimethacrylates (diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, etc.), triacrylates (trimethylolethane triacrylate, trimethylolbutane triacrylate, etc.) ), trimethacrylates (trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, etc.), triallylcyanurate, triallylisocyanurate, diallylmalate, and the like. Note that polyfunctional monomers are difficult to disperse uniformly in polyvinylidene fluoride resin, so the polyfunctional monomers are kneaded into ethylene-vinyl acetate copolymer and mixed uniformly, and this mixture is mixed with polyvinylidene fluoride resin. It is necessary to mix uniformly with a mixer such as a tumbler. A resin composition containing an ethylene-vinyl acetate copolymer, a polyvinylidene fluoride resin, and a polyfunctional monomer is molded into a predetermined shape using an extruder, and then crosslinked by irradiation with ionizing radiation such as an electron beam. Although the present invention is applicable to the production of various crosslinked molded bodies, it is particularly suitable for the production of heat-shrinkable tubes. Heat-shrinkable tubes are manufactured by expanding the tube at a temperature above the softening point or melting point and then cooling it, but the tube cannot be expanded at temperatures above the softening point or melting point because the resin melts. . For this reason, crosslinking is performed to prevent the tube from melting. Crosslinking methods include chemical crosslinking, ionizing radiation crosslinking, etc., but chemical crosslinking is impossible because there is no organic peroxide that can withstand the molding temperature of polyvinylidene fluoride resin. Therefore, in the present invention, crosslinking by irradiation with ionizing radiation is employed. [Examples of the Invention] Resin compositions containing various components as shown in Table 1 were prepared. In this case, the ethylene-vinyl acetate copolymer and the polyfunctional monomer (trimethylolpropane trimethacrylate, triallyl isocyanurate) were uniformly mixed, and then mixed with the polyvinylidene fluoride resin. The above resin composition is formed into a sheet by pressing,
It was crosslinked by electron beam accelerator irradiation. The evaluation results for the sheets of each example are as shown in the lower column of Table 1. The evaluation was based on the following. Combustion test: A 2 mm thick sheet was irradiated with 5 Mrad using a 1.5 MeV electron beam accelerator, and then evaluated based on ASTMD635. Transparency: Visually determined after irradiating a 0.5 mm thick sheet with 5 Mrad using a 1.5 MeV electron beam accelerator. Flexibility (scanto modulus): A 0.5 mm thick sheet was irradiated with 5 Mrad using a 1.5 MeV electron beam accelerator and then tested in accordance with UL224. Judgment is UL224
Compliant with the criteria for flexible type.
【表】【table】
【表】
［発明の効果］
以上説明してきた通り、本発明によれば、可撓
性、透明性および難燃性に優れた架橋成形体を得
ることが可能となる。[Table] [Effects of the Invention] As explained above, according to the present invention, it is possible to obtain a crosslinked molded article having excellent flexibility, transparency, and flame retardancy.
Claims (1)
マを混合し、次いでこの混合物とポリふつ化ビニ
リデン樹脂を混合することにより、エチレン−酢
酸ビニル共重合体20〜80重量％とポリふつ化ビニ
リデン樹脂80〜20重量％を含む樹脂成分100重量
部に対して多官能モノマを0.5〜15重量部含有す
る樹脂組成物を調整し、当該樹脂組成物を成形し
てから電離性放射線の照射により架橋することを
特徴とする照射架橋難燃性透明樹脂成形体の製造
方法。1 By mixing an ethylene-vinyl acetate copolymer and a polyfunctional monomer, and then mixing this mixture with a polyvinylidene fluoride resin, 20 to 80% by weight of the ethylene-vinyl acetate copolymer and 80% by weight of the polyvinylidene fluoride resin are produced. Preparing a resin composition containing 0.5 to 15 parts by weight of a polyfunctional monomer based on 100 parts by weight of a resin component containing ~20% by weight, molding the resin composition, and then crosslinking it by irradiation with ionizing radiation. A method for producing an irradiation-crosslinked flame-retardant transparent resin molded article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP610184A JPS60149630A (en) | 1984-01-17 | 1984-01-17 | Production of radiation-crosslinkable flame-retarding transparent resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP610184A JPS60149630A (en) | 1984-01-17 | 1984-01-17 | Production of radiation-crosslinkable flame-retarding transparent resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60149630A JPS60149630A (en) | 1985-08-07 |
| JPH0334776B2 true JPH0334776B2 (en) | 1991-05-23 |
Family
ID=11629106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP610184A Granted JPS60149630A (en) | 1984-01-17 | 1984-01-17 | Production of radiation-crosslinkable flame-retarding transparent resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60149630A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0687204U (en) * | 1993-05-27 | 1994-12-22 | 昌弘機工株式会社 | Film welding heater for packing machine |
| JP4524599B2 (en) * | 2004-09-28 | 2010-08-18 | 大日本印刷株式会社 | Method for producing foam wallpaper |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4923250A (en) * | 1972-06-23 | 1974-03-01 | ||
| JPS5219746A (en) * | 1975-08-04 | 1977-02-15 | Raychem Corp | Process for production of articles showing ptc demeanour |
-
1984
- 1984-01-17 JP JP610184A patent/JPS60149630A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4923250A (en) * | 1972-06-23 | 1974-03-01 | ||
| JPS5219746A (en) * | 1975-08-04 | 1977-02-15 | Raychem Corp | Process for production of articles showing ptc demeanour |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60149630A (en) | 1985-08-07 |
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